Advertisement

Transition Metal Chemistry

, Volume 9, Issue 8, pp 294–299 | Cite as

Phenolate complexes of iron(III) in dimethylsulphoxide solution

  • Juan Faus
  • José M. Moratal
  • Manuel Castelló
Full Papers

Summary

The formation of complexes between Fe3+ and 2,4-dinitrophenol, 4-nitrophenol and 4-methylphenol is studied in dimethylsulphoxide solution. The reaction proceeds almost to completion and the occurrence, in solution, of complexes with higher stoichiometry than 1∶1 is reported for the first time. The following stability constants are determined (25 °C, 0.1 M KClO4): FeIII-2,4-dinitrophenolate β1=1.8×103, β2=4.4×105; FeIII-4-nitrophenolate β1=1.10×107, β2=2.5×1012 β3=3.9×1016; FeIII-4-methylphenolate β=1.7×1012.

The binding of a phenolate ligand to iron(III) strongly decreases its affinity for other phenolate ligands. The superior σ-donor, 4-methylphenolate (OC6H4Me), only forms a 1∶1 complex, Fe(OC6H4Me)2+. The e.s.r. spectrum of this species clearly prove it is a true iron(III) complex and does not contain iron(II), in opposition to recent claims. However, the complex Fe(OC6H4Me)2+ easily undergoes a ligand-to-metal electron transference. Addition of an excess of 1,10 phenanthroline yields the iron(II) complex [Fe(o-phen)3]2+ instantaneously.

Keywords

Iron Physical Chemistry Phenolate Inorganic Chemistry Electron Transference 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. (1).
    L. Que Jr.,Coord. Chem. Rev., 50, 73 (1983).Google Scholar
  2. (2).
    S. E. Jones, L. E. Leon and D. T. Sawyer,Inorg. Chem., 21, 3692 (1982) and ref. therein.Google Scholar
  3. (3).
    F. Lloret, J. Moratal and J. Faus,An Quim., 77B, 202 (1981).Google Scholar
  4. (4).
    F. Lloret, J. Moratal and J. Faus, unpublished observations.Google Scholar
  5. (5).
    H. Schiff,Ann. Chem. Pharm., 159, 158 (1871).Google Scholar
  6. (6).
    S. A. Koch and M. Millar,J. Am. Chem. Soc., 104, 5255 (1982).Google Scholar
  7. (7).
    E. F. Wesp and W. R. Brode,J. Am. Chem. Soc., 56, 1037 (1934).Google Scholar
  8. (8).
    R. M. Milburn,J. Am. Chem. Soc., 77, 2064 (1955).Google Scholar
  9. (9).
    Z. L. Ernst and F. G. Herring,Trans. Faraday Soc., 61, 454 (1965).Google Scholar
  10. (10).
    R. M. Milburn,J. Am. Chem. Soc., 88, 3224 (1966).Google Scholar
  11. (11).
    R. M. Milburn,J. Am. Chem. Soc., 89, 54 (1967).Google Scholar
  12. (12).
    R. M. Milburn and A. G. Desai,J. Am. Chem. Soc., 91, 1958 (1969).Google Scholar
  13. (13).
    W. A. E. McBryde,Can. J. Chem., 46, 2385 (1968).Google Scholar
  14. (14).
    J. Silver, I. E. G. Morrison and L. V. C. Rees,Inorg. Nucl. Chem. Lett., 15, 433 (1979).Google Scholar
  15. (15).
    R. C. Hider, A. R. Mohd-Nor, J. Silver, I. E. G. Morrison and L. V. C. Rees,J. Chem. Soc. Dalton Trans., 609 (1981).Google Scholar
  16. (16).
    M. Julve, J. Moratal and J. Faus,Rev. Chim. Min., 17, 138 (1980).Google Scholar
  17. (17).
    D. Martin and H. G. Hauthal,Dimethylsulphoxide, Van Nostrand Reinhold, 1975, p. 105.Google Scholar
  18. (18).
    S. Ahrland and N. O. Bjork,Acta Chem. Scand., A30, 249 (1976).Google Scholar
  19. (19).
    A. Sabatini, A. Vacca and P. Gans,Talanta, 21, 53 (1974).Google Scholar
  20. (20).
    J. Chrisment, D. Nicole and J. J. Delpuech,C. R. Acad. Sc. Paris, 286 C, 541 (1978).Google Scholar
  21. (21).
    R. S. Drago,Physical Methods in Chemistry, W. B. Saunders, 1977, p. 493.Google Scholar
  22. (22).
    J. Moratal, M. Julve and J. Faus,Rev. Chim. Min., 19, 72 (1982).Google Scholar
  23. (23).
    H. S. Rossotti,Talanta, 21, 809 (1974).Google Scholar
  24. (24).
    D. F. Evans,J. Chem. Phys., 2003 (1959).Google Scholar

Copyright information

© Verlag Chemie GmbH 1984

Authors and Affiliations

  • Juan Faus
    • 1
  • José M. Moratal
    • 1
  • Manuel Castelló
    • 1
  1. 1.Departamento de Quimica InorgánicaFacultad de Química de la Universidad de ValenciaSpain

Personalised recommendations